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Optical particle counter measurement of marine aerosol hygroscopic growth

A technique is developed for the determination of the hygroscopic growth factor of dry particles with diameter between 0.3 and 0.6 μm and is applied to measurements made during the second Dynamics and Chemistry of Marine Stratocumulus experiment (DYCOMS-II). Two optical particle counters are utilized, one measures the aerosol size spectrum at ambient relative humidity and the other simultaneously dries the aerosol prior to light scattering detection. Growth factors are based on measurements made in the region of the Mie scattering curve where scattered light intensity increases monotonically with dry and wet particle diameter, i.e. D<0.9 μm. Factors influencing the accuracy of the measurement are evaluated, including particle drying, refractive index and shape. Growth factors at 90±3% ambient relative humidity in marine airmasses 400 km west of San Diego, California range between 1.5 and 1.8. This suggests that a significant fraction of the particle mass, between 40 and 70%, is either non-hygroscopic or weakly hygroscopic.
Space-borne measurements of mesospheric magnesium species – a retrieval algorithm and preliminary profiles

We present a joint retrieval as well as first results for mesospheric air density and mesospheric Magnesium species (Mg and Mg+) using limb data from the SCIAMACHY instrument on board the European ENVISAT satellite.considered. These species feature Metallic species like neutral Mg, ionized Mg+ and others (Fe, Si, Li, etc.) ablate from meteoric dust, enter the gas phase and occur at high altitudes (≥70 km). Emissions from these species are clearly observed in the SCIAMACHY limb measurements. These emissions are used to retrieve total and thermospheric column densities as well as preliminary profiles of metallic species in the altitude range of 70–92 km. In this paper, neutral Magnesium as well as its ionized counterpart Mg+ is considered. These species feature resonance fluorescence in the wavelength range 279 and 285 nm and thus have a rather simple excitation process. A radiative transfer model (RTM) for the mesosphere has been developed and validated. Based on a ray tracing kernel, radiances in a large wavelength range from 240–300 nm covering limb as well as nadir geometry can be calculated. The forward model has been validated and shows good agreement with established models in the given wavelength range and a large altitude range. The RTM has been coupled to a retrieval based on Optimal Estimation. Air density is retrieved from Rayleigh backscattered light. Mesospheric Mg and Mg+ number densities are retrieved from their emission signals observed in the limb scans of SCIAMACHY. Other species like iron, silicon, OH and NO can be investigated in principle with the same algorithm. Based on the retrieval presented here, SCIAMACHY offers the opportunity to investigate mesospheric species on a global scale and with good vertical resolution for the first time.
Combustion particulate emissions in Africa: regional climate modeling and validation

Africa, as a major aerosol source in the world, plays a key role in regional and global geochemical cycles and climate change. Combustion carbonaceous particles, central in this context through their radiative and hygroscopic properties, require ad hoc emission inventories. These inventories must incorporate fossil fuels FF (industries, traffic,...), biofuels BF (charcoal, wood burning,... quite common in Africa for domestic use), and biomass burning BB regularly occurring over vast areas all over the African continent. This latter, subject to rapid massive demographic, migratory, industrial and socio-economic changes, requires continuous emission inventories updating, so as to keep pace with this evolution. Two such different inventories, L96 and L06 with main focus on BB emissions, have been implemented for comparison within the regional climate model RegCM3 endowed with a specialized carbonaceous aerosol module. Resulting modeled black carbon BC and organic carbon OC fields have been compared to past and present composite data set available in Africa. This data set includes measurements from intensive field campaigns (EXPRESSO 1996, SAFARI 2000), from the IDAF/DEBITS surface network and from MODIS, focused on selected west, central and southern African sub-domains. This composite approach has been adopted to take advantage of possible combinations between satellite high-resolution coverage of Africa, regional modeling, use of an established surface network, together with the patchy detailed knowledge issued from past short intensive regional field experiments. Stemming from these particular comparisons, one prominent conclusion is the need for continuous detailed time and spatial updating of combustion emission inventories apt to reflect the rapid transformations of the African continent.
Total observed organic carbon (TOOC) in the atmosphere: a synthesis of North American observations

Measurements of organic carbon compounds in both the gas and particle phases made upwind, over and downwind of North America are synthesized to examine the total observed organic carbon (TOOC) in the atmosphere over this region. These include measurements made aboard the NOAA WP-3 and BAe-146 aircraft, the NOAA research vessel Ronald H. Brown, and at the Thompson Farm and Chebogue Point surface sites during the summer 2004 ICARTT campaign. Both winter and summer 2002 measurements during the Pittsburgh Air Quality Study are also included. Lastly, the spring 2002 observations at Trinidad Head, CA, surface measurements made in March 2006 in Mexico City and coincidentally aboard the C-130 aircraft during the MILAGRO campaign and later during the IMPEX campaign off the northwestern United States are incorporated. Concentrations of TOOC in these datasets span more than two orders of magnitude. The daytime mean TOOC ranges from 4.0 to 456 μgC m−3 from the cleanest site (Trinidad Head) to the most polluted (Mexico City). Organic aerosol makes up 3–17% of this mean TOOC, with highest fractions reported over the northeastern United States, where organic aerosol can comprise up to 50% of TOOC. Carbon monoxide concentrations explain 46 to 86% of the variability in TOOC, with highest TOOC/CO slopes in regions with fresh anthropogenic influence, where we also expect the highest degree of mass closure for TOOC. Correlation with isoprene, formaldehyde, methyl vinyl ketone and methacrolein also indicates that biogenic activity contributes substantially to the variability of TOOC, yet these tracers of biogenic oxidation sources do not explain the variability in organic aerosol observed over North America. We highlight the critical need to develop measurement techniques to routinely detect total gas phase VOCs, and to deploy comprehensive suites of TOOC instruments in diverse environments to quantify the ambient evolution of organic carbon from source to sink.
Aerosol extinction profiles at 525 nm and 1020 nm derived from ACE imager data: comparisons with GOMOS, SAGE II, SAGE III, POAM III, and OSIRIS

The Canadian ACE (Atmospheric Chemistry Experiment) mission is dedicated to the retrieval of a large number of atmospheric trace gas species using the solar occultation technique in the infrared and UV/visible spectral domain. However, two additional solar disk imagers (at 525 nm and 1020 nm) were added for a number of reasons, including the retrieval of aerosol and cloud products. In this paper, we present first comparison results for these imager aerosol/cloud optical extinction coefficient profiles, with the ones derived from measurements performed by 3 solar occultation instruments (SAGE II, SAGE III, POAM III), one stellar occultation instrument (GOMOS) and one limb sounder (OSIRIS). The results indicate that the ACE imager profiles are of good quality in the upper troposphere/lower stratosphere, although the aerosol extinction for the visible channel at 525 nm contains a significant negative bias at higher altitudes, while the relative differences indicate that ACE profiles are almost always too high at 1020 nm. Both problems are probably related to ACE imager instrumental issues.
Technical note: Analytical formulae for the critical supersaturations and droplet diameters of CCN containing insoluble material

In this paper, we consider the cloud drop activation of aerosol particles consisting of water soluble material and an insoluble core. Based on the Köhler theory, we derive analytical equations for the critical diameters and supersaturations of such particles. We demonstrate the use of the equations by comparing the critical supersaturations of particles composed of ammonium sulfate and insoluble substances with those of model organic particles with varying molecular sizes.
Continental outflow from the US to the upper troposphere over the North Atlantic during the NASA INTEX-NA Airborne Campaign

A case of continental outflow from the United States (US) was examined using airborne measurements from NASA DC-8 flight 13 during the Intercontinental Chemical Transport Experiment – North America (INTEX-NA). Mixing ratios of methane (CH4) and carbon monoxide (CO) at 8–11 km altitude over the North Atlantic were elevated to 1843 ppbv and 134 ppbv respectively, while those of carbon dioxide (CO2) and carbonyl sulfide (COS) were reduced to 372.4 ppmv and 411 pptv respectively. In this region, urban and industrial influences were evidenced by elevated mixing ratios and good linear relationships between urban and industrial tracers compared to North Atlantic background air. Moreover, low mixing ratios and a good correlation between COS and CO2 showed a fingerprint of terrestrial uptake and minimal dilution during rapid transport over a 1–2 day time period. Analysis of synoptic conditions, backward trajectories, and photochemical aging estimates based on C3H8/C2H6 strongly suggested that elevated anthropogenic tracers in the upper troposphere of the flight region were the result of transport via convection and warm conveyor belt (WCB) uplifting of boundary layer air over the southeastern US. This mechanism is supported by the similar slope values of linear correlations between long-lived (months) anthropogenic tracers (e.g., C2Cl4 and CHCl3) from the flight region and the planetary boundary layer in the southeastern US. In addition, the aircraft measurements suggest that outflow from the US augmented the entire tropospheric column at mid-latitudes over the North Atlantic. Overall, the flight 13 data demonstrate a pervasive impact of US anthropogenic emissions on the troposphere over the North Atlantic.
Reversible and irreversible processing of biogenic olefins on acidic aerosols

Recent evidence has suggested that heterogeneous chemistry of oxygenated hydrocarbons, primarily carbonyls, plays a role in the formation of secondary organic aerosol (SOA); however, evidence is emerging that direct uptake of alkenes on acidic aerosols does occur and can contribute to SOA formation. In the present study, significant uptake of monoterpenes, oxygenated monoterpenes and sesquiterpenes to acidic sulfate aerosols is found under various conditions in a reaction chamber. Proton transfer mass spectrometry is used to quantify the organic gases, while an aerosol mass spectrometer is used to quantify the organic mass uptake and obtain structural information for heterogeneous products. Aerosol mass spectra are consistent with several mechanisms including acid catalyzed olefin hydration, cationic polymerization and organic ether formation, while measurable decreases in the sulfate mass on a per particle basis suggest that the formation of organosulfate compounds is also likely. A portion of the heterogeneous reactions appears to be reversible, consistent with reversible olefin hydration reactions. A slow increase in the organic mass after a fast initial uptake is attributed to irreversible reactions, consistent with polymerization and organosulfate formation. Uptake coefficients (γ) were estimated for a fast initial uptake governed by the mass accommodation coefficient (α) and ranged from 1×10-6-2.5×10-2. Uptake coefficients for a subsequent slower reactive uptake ranged from 1×10-7-1×10-4. These processes may potentially lead to a considerable amount of SOA from the various biogenic hydrocarbons under acidic conditions, which can be highly significant for freshly nucleated aerosols, particularly given the large array of atmospheric olefins.
Assessment of high (diurnal) to low (seasonal) frequency variations of isoprene emission rates using a neural network approach

Using a statistical approach based on artificial neural networks, an emission algorithm (ISO-LF) accounting for high to low frequency variations was developed for isoprene emission rates. ISO-LF was optimised using a data base (ISO-DB) specifically designed for this work, which consists of 1321 emission rates collected in the literature and 34 environmental variables, measured or assessed using National Climatic Data Center or National Centers for Environmental Predictions meteorological databases. ISO-DB covers a large variety of emitters (25 species) and environmental conditions (10° S to 60° N). When only instantaneous environmental regressors (instantaneous air temperature T0 and photosynthetic photon flux density L0) were used, a maximum of 60% of the overall isoprene variability was assessed with the highest emissions being strongly underestimated. ISO-LF includes a total of 9 high (instantaneous) to low (up to 3 weeks) frequency regressors and accounts for up to 91% of the isoprene emission variability, whatever the emission range, species or climate investigated. ISO-LF was found to be mainly sensitive to air temperature cumulated over 3 weeks (T21) and to L0 and T0 variations. T21, T0 and L0 only accounts for 76% of the overall variability.
Factors influencing the large-scale distribution of Hg° in the Mexico City area and over the North Pacific

Gas-phase elemental mercury (Hg°) was measured aboard the NASA DC-8 aircraft during the Intercontinental Chemical Transport Experiment Phase B (INTEX-B) campaign in spring 2006. Flights were conducted around Mexico City and on two subsequent deployments over the North Pacific based out of Honolulu, Hawaii and Anchorage, Alaska. Data obtained from 0.15–12 km altitude showed that Hg° exhibited a relatively constant vertical profile centered around 100 ppqv. Highly concentrated pollution plumes emanating from the Mexico City urban agglomeration revealed that mixing ratios of Hg° as large as 500 ppqv were related to combustion tracers such as CO, but not SO2 which is presumably released locally from coal burning, refineries, and volcanoes. Our analysis of Mexico City plumes indicated that widespread multi-source urban/industrial emissions may have a more important influence on Hg° than specific point sources. Over the Pacific, correlations with CO, CO2, CH4, and C2Cl4 were diffuse overall, but recognizable on flights out of Anchorage and Honolulu. In distinct plumes originating from the Asian continent the Hg°- CO relationship yielded an average value of ~0.56 ppqv/ppbv, in good agreement with previous findings. A prominent feature of the INTEX-B dataset was frequent total depletion of Hg° in the upper troposphere when stratospherically influenced air was encountered. Ozone data obtained with the differential absorption lidar (DIAL) showed that the stratospheric impact on the tropospheric column was a common and pervasive feature on all flights out of Honolulu and Anchorage. We propose that this is likely a major factor driving large-scale seasonality in Hg° mixing ratios, especially at mid-latitudes, and an important process that should be incorporated into global chemical transport models.